TECHNICAL NOTE

Selecting an appropiate particle absorption for

laser diffraction particle size calculations

Laser diffraction instruments obtain particle size information by measuring the

PARTICLE SIZE angular dependence of the intensity of light scattered by particles illuminated in
a laser beam. An optical model is then used to interpret this scattering data and
hence calculate a particle size distribution. The scattering model that is generally
used is Mie theory. This is the scattering model which is recommended by the
international standard for laser diffraction (ISO13320-1), especially when particles
smaller than 50 μm in size are being measured.

Mie theory is a general solution of Maxwell's equations for the interaction of light
with matter. When applied to laser diffraction measurements, it predicts both
the intensity of light scattered from the particle surface, as well as the behavior
of light which is transmitted and refracted through the particle, as illustrated in
Figure 1. In order to use this theory correctly, the complex refractive index for the
material being measured is required. This complex refractive index comprises
a real and imaginary part. The real part of the refractive index is required to
predict the diffraction from the particle surface, and can be determined from
refractometer measurements, microscope observations or can be estimated
using empirical methods [2,3]. The imaginary refractive index accounts for the
attenuation of light as it passes through the particle, and is commonly referred
to as the absorption of the material. This application note will look in more detail
at the absorption and how the correct absorption value can be determined for a
sample.

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Figure 1 : Scattering predicted by the Mie scattering model.

Particle absorption
The absorption of a material is dependent on its molecular make-up, and
whether there are any chromophores present within the molecular structure
which cause light to be absorbed at a wavelength of the light source used in
the laser diffraction measurements. Pigments are good examples of materials
which contain strong chromophores, as it is the absorption of light at specific
wavelengths which gives rise to their color. Typically, laser diffraction systems
combine measurement made at red (600-700nm) and blue (400-500nm)
wavelengths. If a material contains a chromophore which causes light to be
absorbed within the wavelength ranges, the absorption used in the Mie Model will
need to be high (>0.1).

Although the molecular properties of the material are important in defining

the absorption used in the laser diffraction analysis, ISO13320-1 highlights the
fact that the physical nature of the particles also needs to be considered. In
particular, if the particles have a rough surface structure, or have a complex
internal structure, the absorption will be higher than that predicted based
on spectroscopic analysis of the material. For this reason, spectroscopic
measurement of the material's absorption often does not yield the correct
absorption value for use in the laser diffraction analysis.

Obtaining realistic absorption values

For the purposes of a laser diffraction measurement, the absorption of a material
generally only has to be specified to an accuracy of an order of magnitude, for
example 1 or 0.1. If it is possible to look at the particles under a microscope, then
their appearance can often be used to estimate a value for the absorption, as
shown in Table 1.

Table 1: Appearance of particles

2 Selecting an appropiate particle absorption for laser diffraction particle size calculations
TECHNICAL NOTE

Appearance Imaginary RI Example

0 Latices

0.001 Emulsions

0.01 Crystalline milled powders

0.1 Slightly colored powders

1.0 + Highly colored powders

Another method which can be used to determine the absorption of a sample

relies on the laser diffraction measurement itself. One of the parameters

3 Selecting an appropiate particle absorption for laser diffraction particle size calculations
TECHNICAL NOTE

calculated by the Mastersizer analysis is the volume concentration (Cv) of particles

being measured. This is calculated based on the measurement of laser light
obscuration, using Beer-Lambert's law.

Beer-Lambert's law describes the relationship between the absorption of light

passing through a material and the properties of that material. It states that the
intensity of light transmitted through a material is dependent on the material's
absorption coefficient and the distance which the light travels through the
material. The absorption coefficient itself is dependent on the wavelength of
light and the imaginary part of refractive index. It is this dependence which will
allow us to use the Mastersizer's measurement of the volume concentration to
determine the correct value of the imaginary refractive index.

Experimental
In this application note the absorption of a calcium carbonate sample will be
determined.

In order to obtain a first estimate of the absorption, the sample was dispersed in
water and then observed under a microscope (figure 2). The images show that the
particles appear

Figure 2 : Images of calcium carbonate particles (taken using Sysmex FPIA).

transparent but are not spherical and have some surface roughness. Therefore,
relating back to Table 1, this would suggest that the absorption is between 0.1
and 0.01.

This estimate of the value of the absorption can be tested by measuring a

known concentration of the sample and comparing this known value to the
value calculated by the Mastersizer analysis. Three different masses of calcium

4 Selecting an appropiate particle absorption for laser diffraction particle size calculations
TECHNICAL NOTE

carbonate, 6.1mg, 13.3mg, 20.7mg, were therefore added to the known volume
of liquid in the Mastersizer's dispersion unit in order to make up the three known
suspension concentrations. The scattering data collected for each suspension
were then analyzed using a range of values for the absorption. The refractive
index used for calcium carbonate was 1.57 [1] and the values of absorption used
were 1, 0.1, 0.01 and 0.01. The particle size distributions calculated using these
values are shown in Figure 3.

From these analyses the calculated percentage volume concentration can be

plotted against the known volume concentration for each value of the absorption.
A linear fit is then applied to each data set. The gradient of the linear fit can
then be used to determine which value for the absorption gives the most direct
relationship between the real and calculated concentration (the gradient closest
to 1). In this case a good agreement occurs using absorption values of 0.01 and
0.1.

Assessing the data fit

It is possible to refine the selection of the absorption by looking at how well the
Mie Model predicts the scattering data collected by the Mastersizer system when
using different absorption values.

In order to interpret the scattering data from a sample to give particle size
information, the Mie scattering model is used. Unfortunately this model works
in the opposite direction than required, predicting the scattering pattern for a
known particle size distribution. Hence, in the laser diffraction analysis, Mie theory
must be used 'backwards', in an iterative process, to derive the size distribution
from the measured scattering data. This process is as follows; the scattering data
from the sample is measured, an initial guess at the size distribution is made. The
Mie model can then be used generate a scattering pattern, and any differences
between the measured scattering and the calculated scattering can then be used
to adjust the initial guess at the size distribution. This process is repeated until the
differences between the measured and calculated scattering is minimized and the
final size distribution is reported.

In addition to reporting the final size distribution, the Mastersizer software

reports the measured scattering data and the calculated scattering data derived
from the Mie

5 Selecting an appropiate particle absorption for laser diffraction particle size calculations
TECHNICAL NOTE

Figure 3: Particle size distributions

Figure 4: Measured concentration vs. known concentration.

model, allowing the user to asses how well the model has been able to fit the
data. Figure 5 shows the fit to the scattering data for the calcium carbonate
sample using an absorption of 0.1. The detectors which are most important when
assessing the absorption value are channels 51 and 52. The response for these
detectors relates to light extinction by the sample. If the value of the absorption
6 Selecting an appropiate particle absorption for laser diffraction particle size calculations
TECHNICAL NOTE

used in the analysis is incorrect then there will be a misfit between the calculated
and measured scattering data on these channels.

From Figure 5 it can be seen that the output of the Mie model predicts too high
a signal on channels 51 and 52 when an absorption of 0.1 is used. This suggests
that the absorption is too high. Recalculating the data with a lower value of
the absorption, 0.01, gives the data fit shown in Figure 6, which shows a much
better agreement between the measured and calculated data on all detectors.
Therefore, for this calcium carbonate sample, the correct value to be used for the
absorption is 0.01.

Conclusions
The volume concentration as calculated by the by the Mastersizer analysis can
be used to determine the correct absorption value for a sample. This can be
done by measuring a known sample concentration and comparing that to the
calculated value. This has been tested for a calcium carbonate sample, where
measurements were made at three known concentrations. By comparing these
known concentrations to the calculated concentrations using absorption values of
1, 0.1, 0.01 and 0.001 the agreement was found to be best at around 0.1 and 0.01.
Then, by inspecting the fit to the data using these two values of the absorption,
the fit was found to be best using 0.01. Therefore, by using these two

Figure 5 : Fit to the scattering data using an absorption of 0.1

Figure 6 : Fit to the scattering data using an absorption of 0.01

methods the correct value for the absorption was found to be 0.01. This
conclusion was also supported by initial microscope observations.

7 Selecting an appropiate particle absorption for laser diffraction particle size calculations
TECHNICAL NOTE

References
[1] ISO13320 (1999). Particle Size Analysis - Laser Diffraction Methods. Part 1:
General Principles.
[2] Rapid refractive index determination for pharmaceutical actives (MRK529-03)
[3] Empirical methods for estimating refractive index values (MRK843-01)

8 Selecting an appropiate particle absorption for laser diffraction particle size calculations
 TECHNICAL NOTE

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